Method for producing coated substrates, coated substrates and use thereof

ABSTRACT

The present disclosure relates to coated non-metallic substrates and coated metallic substrates and methods for producing such coated substrates. A variant of the method is characterized in that a mat or glossy coating is underneath a metallic layer obtained in some eases by way of vapor deposition and/or sputtering. In another variant, the metallic layer is sufficiently thin so that it remains transparent or translucent to visible light. The coated substrates may include multiple layers such as metallic layers, polysiloxane layers, a color layer, a conversion layer, a primer layer, and/or a transparent or colored layer. An application system for applying a metallic layer to at least one surface of a substrate may include a plasma generator and/or a corona system for treating one or more layers by plasma treatment and/or corona treatment.

DESCRIPTION

The present invention relates to methods for manufacturing coatedsubstrates, coated substrates and the use of these coated substrates.

Metallic and non-metallic components are frequently coated in order toproduce a smooth and/or shining surface. As a rule, this involvesmultilayer coating systems. As well as the desire of obtaining a surfacewith a high-quality attractive appearance, the intention with suchcoating systems is regularly also to achieve significant corrosionprotection. Not unusually, long-term corrosion protection is brought tonothing by mechanical damage. In many cases, even very slight mechanicaldamage causes corrosion on coated surfaces. As well as discolouration,this can also result in infiltration phenomena. Not unusually, this inturn leads to the flaking away of areas of coating. There has been nolack of experiments aimed at rendering coated shining surfaces resistantto corrosion. DE 123 765 A1, for example, describes a method forproducing a corrosion protection layer on a metallic surface, in which asol based on silicon compounds, an aminoalkyl-functionalizedalkoxysilane or a conversion product of the two aforesaid components isused.

According to DE 38 33 119 C2, a corrosion-protected chromatized metallicsurface which adheres very well to a substrate is obtained by anelectrodeposition coating being deposited directly onto the chromatinglayer, without intermediate drying.

Corrosion protection coatings for metallic substrates nevertheless stillexhibit a substantial potential for improvement with regard to adherenceand corrosion protection, in particular with mass-produced products, inparticular those with complex geometries.

The production of coated metallic-appearance substrates with a matt orcoloured appearance at low cost and at the same time in high quality hasalso been shown to be no triviality.

The present invention is therefore based on the object of providingcoated substrates which are no longer impaired by the disadvantages ofthe prior art, and which, in particular with regard to mass production,provide coated products with good corrosion protection and/or very goodadherence properties, and which also have a matt or coloured appearance.Here, it is also intended to provide such coated products which do notimmediately exhibit infiltration phenomena in the event of mechanicalsurface damage, in particular not associated with the flaking away oflayers.

Accordingly, a method has been found for manufacturing a coatednon-metallic substrate, in particular a plastic substrate, comprising

-   a) provision of a non-metallic substrate, in particular a plastic    substrate, with at least one surface which is capable of being    coated at least in part areas,-   b) provision of an application system for the application of a    metallic layer, in particular a vacuum vapour deposition system or    sputtering system,-   c) provision of at least one plasma generator and/or at least one    corona system, in particular within the application system for the    application of a metallic layer, such as the vacuum vapour    deposition system or sputtering system, or as a component thereof,-   d) optionally, plasma treatment with the plasma generator and/or    corona treatment of the non-metallic substrate, in particular    plastic substrate, or of the coatable surface of the non-metallic    substrate, in particular plastic substrate,-   e) optionally, treating of the non-metallic substrate, in particular    plastic substrate, obtained according to step a) or d), or of the    coatable surface of the non-metallic substrate, in particular    plastic substrate, with at least one organosilicon compound, in    particular by use of plasma polymerization, thus forming a    polysiloxane layer,-   f) optionally, plasma treatment with the plasma generator and/or    corona treatment of the polysiloxane layer in accordance with step    e),-   g) optionally, applying at least one, optionally coloured, primer    layer onto the non-metallic substrate, in particular plastic    substrate, or onto the coatable surface of the non-metallic    substrate, in particular plastic substrate, in accordance with    step a) or d), or onto the polysiloxane layer in accordance with    step e) or f),-   h) optionally, plasma treatment with the plasma generator and/or    corona treatment of the primer layer in accordance with step g),-   i) optionally, treating the primer layer obtained according to    step g) or h) with least one organosilicon compound, in particular    by use of plasma polymerization, thus forming a polysiloxane layer,-   j) optionally, plasma treatment with the plasma generator and/or    corona treatment of the polysiloxane layer in accordance with step    i),-   j-k) applying at least one matt, in particular colour, coating, such    as a matt lacquer, in particular with gloss grade “medium gloss”    (G2) or preferably with gloss grade “matt” (G3), respectively    determined according to DIN EN ISO 2813:2014 (issue date: 2015-02)    or applying at least one gloss, in particular colour, coating, such    as a gloss lacquer, in particular with gloss grade “glossy” (G1),    determined according to DIN EN ISO 2813:2014 (issue date: 2015-02),    preferably applying the matt coating,-   k) applying at least one metallic layer, containing or consisting of    one first metal selected from the group consisting of aluminium,    silver, gold, lead, vanadium, manganese, magnesium, iron, cobalt,    nickel, copper, chromium, palladium, molybdenum, tungsten, platinum,    titanium, zirconium and zinc, in particular aluminium, or containing    or consisting of a first metal alloy from the group consisting of    brass, bronze, steel, in particular stainless steel, aluminium,    manganese and titanium alloys, with the application system, in    particular by use of vapour deposition and/or sputtering technology,    to the coating according to steps j-k),-   l) optionally, plasma treatment with the plasma generator and/or    corona treatment of the metallic layer in accordance with step k),-   m) preferably treating the metallic layer obtained according to    step k) or l) with at least one organosilicon compound, in    particular by use of plasma polymerization, thus forming a    polysiloxane layer,-   n) preferably plasma treatment with the plasma generator and/or    corona treatment of the polysiloxane layer in accordance with step    m), and-   o) applying at least one, in particular transparent and/or coloured,    overcoat onto the layer in accordance with steps k), l), m) or n),    in particular onto the treated polysiloxane layer in accordance with    step n).

With the method described, the metallic layer, in particular thealuminium layer, is preferably applied in step k) in a thickness, inparticular vapour deposited or sputtered on, so that the metallic layer,in particular also in accordance with steps l), m), n), and/or o), isnot transparent and not translucent for visible light. It hassurprisingly been shown that although the metallic layer is applied in athickness that is not translucent or even not transparent for visiblelight, the final product obtained according to this method neverthelessprovides a matt appearance. The matt character is accordinglytransferred to the applied metallic layer. As a result, the non-metallicsubstrate obtains according to this method, in particular coated plasticproducts, are given a very elegant appearance. Here, it is alsoadvantageous that they not only stand out for a high degree of corrosionprotection, but also, as is otherwise frequently the case among productswith matt surfaces, mechanical influences on the surface do not impairthe appearance of this surface. For example, no abrasion or no change tothe matt appearance is observed in the places where mechanical influencewas made. In a corresponding manner, through the use of a glossycoating, the gloss of the metallic layer applied over it can again beintensified. Any colours required can be used for the creation of a mattor glossy coating. If the metallic layer is applied opaquely, in otherwords such that it is not transparent for visible light and also nottranslucent, only the matt or glossy character of the coating istransferred onto the applied metallic layer, but not also the colour ofthis coating. Persons skilled in the art are familiar with matt andglossy coatings. Matt coatings can for example be obtained using aso-called matting paste.

In the sense of the present invention, such a metallic layer, which isin particular applied using vapour deposition or sputtering technology,is not transparent or translucent, which has a thickness of at least 60,for example in the region of 60 nm to 120 nm, preferably in the range of75 nm to 110 nm.

Alternatively, in a further, albeit not preferred embodiment, it ispossible to apply the metallic layer, in particular the aluminium layer,in step k) in a thickness, in particular using vapour deposition orsputtering, such that said layer is transparent or translucent forvisible light. The transparent or translucent metallic layer herepreferably has an average, in particular absolute, thickness in therange of 1 nm to 50 nm, preferably in the range of 10 nm to 40 nm, andparticularly preferred in the range of 15 nm to 30 nm.

The object that forms the basis of the invention is further attained byuse of a method for producing a coated, non-metallic substrate, inparticular a plastic substrate, comprising

-   a) provision of a non-metallic substrate, in particular a plastic    substrate, with at least one surface which is capable of being    coated at least in part areas,-   b) provision of an application system for the application of a    metallic layer, in particular a vacuum vapour deposition system or    sputtering system,-   c) provision of at least one plasma generator and/or at least one    corona system, in particular within the application system for the    application of a metallic layer, such as the vacuum vapour    deposition system or sputtering system, or as a component thereof,-   d) optionally, plasma treatment with the plasma generator and/or    corona treatment of the non-metallic substrate, in particular    plastic substrate, or of the coatable surface of the non-metallic    substrate, in particular plastic substrate,-   e) optionally, treating of the non-metallic substrate, in particular    plastic substrate, obtained according to step a) or d), or of the    coatable surface of the non-metallic substrate, in particular    plastic substrate, with at least one organosilicon compound, in    particular by use of plasma polymerization, thus forming a    polysiloxane layer,-   f) optionally, plasma treatment with the plasma generator and/or    corona treatment of the polysiloxane layer in accordance with step    e),-   g) optionally, applying at least one, in particular coloured, primer    layer onto the non-metallic substrate, in particular plastic    substrate, or onto the coatable surface of the non-metallic    substrate, in particular plastic substrate, in accordance with    step a) or d), or onto the polysiloxane layer in accordance with    step e) or f),-   h) optionally, plasma treatment with the plasma generator and/or    corona treatment of the primer layer in accordance with step g),-   i) optionally, treating the primer layer obtained according to    step g) or h) with least one organosilicon compound, in particular    by use of plasma polymerization, thus forming a polysiloxane layer,-   j) optionally, plasma treatment with the plasma generator and/or    corona treatment of the polysiloxane layer in accordance with step    i),-   jj-kk) preferably applying at least one colour layer onto the    non-metallic substrate or the coatable surface of the non-metallic    substrate according to step a) or d) or onto the polysiloxane layer    according to step e) or f), or onto the primer layer according to    step g) or h), or onto the polysiloxane layer according to step i)    or j),-   k′) applying at least one metallic layer, containing or consisting    of a first metal, selected from the group consisting of aluminium,    silver, gold, lead, vanadium, manganese, magnesium, iron, cobalt,    nickel, copper, chromium, palladium, molybdenum, tungsten, platinum,    titanium, zirconium and zinc, in particular aluminium, or containing    or consisting of a first metal alloy, selected from the group    consisting of brass, bronze, steel, in particular special or    stainless steel, alloys of aluminium, magnesium and titanium, with    the application system, in particular by use of vapour deposition    and/or sputtering technology, onto the non-metallic substrate, in    particular plastic substrate, or onto the coatable surface of the    non-metallic substrate, in particular plastic substrate, in    accordance with step a) or d), or onto the polysiloxane layer in    accordance with step e) or f), or onto the primer layer in    accordance with step g) or h), or onto the polysiloxane layer in    accordance with step i) or j), or onto the colour layer according to    step jj-kk), whereby the metallic layer, in particular the aluminium    layer, is applied in a thickness, in particular using vapour    deposition or sputtering technology, such that the metallic layer,    in particular also in accordance with step l), m), n) and/or o), is    transparent or translucent for visible light,-   l) optionally, plasma treatment with the plasma generator and/or    corona treatment of the metallic layer in accordance with step k′),-   m) preferably treating the metallic layer obtained according to step    k′) or l) with at least one organosilicon compound, in particular by    use of plasma polymerization, thus forming a polysiloxane layer,-   n) preferably plasma treatment with the plasma generator and/or    corona treatment of the polysiloxane layer in accordance with step    m), and-   o) applying at least one, in particular transparent and/or coloured,    overcoat onto the layer in accordance with steps k′), l), m) or n),    in particular onto the treated polysiloxane layer in accordance with    step n).

The transparent or translucent metallic layer in step k′) herepreferably has an average, in particular absolute, thickness in therange of 1 nm to 50 nm, preferably in the range of 10 nm to 40 nm, andparticularly preferred in the range of 15 nm to 30 nm.

With the method described above, in a preferred embodiment, steps m) andn) are conducted prior to step o).

Adjacent to the transparent or translucent metallic layer (layer k′), onthe other side of the overcoat, preferably, the colour layer (layerjj-kk), the colour or coloured polysiloxane layer, the colour orcoloured primer layer or the colour or coloured non-metallic substrateare placed. In this manner, very high-quality appearance coating systemsare obtained. For example, through the use of a black colour layer or ablack coloured non-metallic substrate, which are placed on thetransparent or translucent metallic layer, the impression of a blackchromium layer can be created.

With the two method variants described above for producing coatednon-metallic substrates, e.g. steps d), e) and f) are only optional. Inindividual cases, they can contribute to improved adherence andincreased corrosion protection. The same applies to the optional stepi). It has shown for some applications that it is of advantage if apolysiloxane layer is present on both sides of the metallic layer, inparticular a plasma-generated polysiloxane layer, which in each case haspreferably been subjected to a plasma treatment and/or a coronatreatment, in particular plasma treatment.

The optional method variant of applying a primer layer is particularlywell-suited for non-metallic substrates, in particular plasticsubstrates, with a surface which exhibits uneven areas or which is ofinferior quality.

With the two methods described above for coating non-metallic substrate,in particular plastic substrates, such method variants have been shownto be advantageous in which

steps g), h), j-k), k), m), n) and o) or g), h), k′), m), n) and o) org), h), jj-kk), k′), m), n) and o) respectively, in particular directly,follow on from each other, in particular excluding steps d), e) and/orf) or using step d) and excluding step e) and f), or

steps g), h), i), j-k), k), m), n) and o) or g), h), i), k′) m), n) ando) or g), h), i), k!), m), n) and o) respectively, in particulardirectly, follow on from each other, in particular excluding steps d),e) and/or f) or using step d) and excluding step e) and f), or

steps d), e), f), j-k), k), m), n) and o) or d), e), f), k′), m), n) ando) or d), e), f), jj-kk), k′), m), n) and o) respectively, in particulardirectly, follow each other or steps d), e), f), i), j-k), k), m), n)and o) or d), e), f), i), k′), m), n) and o) or d), e), f), i), jj-kk),k′), m), n) and o) respectively, in particular directly, follow eachother, or steps d), e), f), g), j-k), k), m), n) and o) or d), e), f),g), k′), m), n) and o) or d), e), f), g), jj-kk), k′), m), n) and o)respectively, in particular directly, follow each other, or

steps d), e), t), g), i), j-k), k), m), n) and o) or d), e), f), g), i),k′), m), n) and o) or d), e), f), g), i), jj-kk), k′), m), n) and o)respectively, in particular directly, follow each other.

In a preferred embodiment, it is provided that in each case, before thestep of applying the metallic layer k) or k′), the application of an inparticular plasma-generated polysiloxane layer (step i)) can beprovided. The method variant described heretofore can be applied, inparticular, with faultless non-metallic substrates, in particularplastic substrates with faultless smooth surfaces.

In a particularly purposeful embodiment, in particular as specifiedheretofore, the layer onto which the metallic layer is applied inaccordance with step k) or k′), is subjected to a plasma treatment withthe plasma generator and/or a corona treatment (e.g. steps j), f) ord)).

It has proved to be of advantage for the method steps referred toheretofore to be applied essentially immediately after one another. Thismeans, in particular, that an extended dwell period after the plasmatreatment steps should be avoided. Rather, it is of advantage if thesubsequent method step follows directly. It has also shown that it isnot generally necessary for further method steps to be interspersedbetween the method steps referred to heretofore.

In one preferred embodiment, it has also proved to be advantageous, inparticular with regard to good adherence and corrosion protection, ifthe non-metallic substrate, in particular the plastic substrate, issubjected to a plasma treatment and/or corona treatment, in particularplasma treatment (step d)).

Suitable non-metallic substrates comprise glass, ceramic, compositefibre materials, carbon materials, plastic, in particular a preferablycoloured plastic, moulded part or a preferably coloured plastic,coating, or wood, in particular wood material panels. Suitable woodmaterial panels comprise e.g. plywood or sandwich panels, chip materialpanels, OSB panels, MDF panels, fibre material panels, wood materialpanels made of solid wood or minerally-bonded wood material panels. MDFpanels have been shown to be particularly advantageous, such as also ina coloured form. This can for example be achieved by mixing colouredsynthetic polymer materials. Wood substrates such as wood materialpanels, e.g. MDF panels, can stand out through surface restructuring,e.g. in the form of a grain pattern. Non-metallic substrates in thesense of the invention accordingly also comprise coloured non-metallicsubstrates.

The method according to the invention described here is particularlywell-suited for coating plastic substrates for the purpose of obtainingdurable high-gloss products. Suitable plastic substrates comprise orconsist of, for example, PVC, polyurethanes, polyacrylates, polyesters,e.g. PBT and PET, polyolefins, in particular polypropylene,polycarbonates, polyamides, polyphenylene ethers, polystyrene, styrene(co)polymers, such as ABS, SAN, ASA or MABS, polyoxyalkylenes, e.g. POM,teflon and polymer blends, in particular ABS/PPE, ASA/PPE, SAN/PPEand/or ABS/PC blends. Plastic substrates in the sense of the inventionalso comprise coatings made of a plastic material, such as MDF panelscoated with a plastic material.

The object on which the invention is based is further achieved by amethod for manufacturing a coated metallic substrate, comprising

-   A) provision of a metallic substrate with at least one surface which    is capable of being coated at least in part areas,-   B) provision of an application system for the application of a    metallic layer, in particular a vacuum vapour deposition system,-   C) provision of at least one plasma generator and/or at least one    corona system, in particular within the application system for the    application of a metallic layer, such as the vacuum vapour    deposition system or the sputtering system, or as a component    thereof,-   D) optionally, cleaning of the metallic substrate or of the coatable    surface of the metallic substrate,-   E) optionally, applying at least one metallic layer, containing or    consisting of a second metal, selected from the group consisting of    titanium, hafnium and zirconium, in particular zirconium, or of a    second metal alloy, selected from the group consisting of alloys of    titanium, hafnium and zirconium, with the application system, in    particular by use of vapour deposition and/or sputtering technology,    onto the metallic substrate or the coatable surface of the metallic    substrate in accordance with step A) or D),-   F) optionally, plasma treatment with the plasma generator and/or    corona treatment of the metallic substrate or of the coatable    surface of the metallic substrate in accordance with step A) or D),    or of the metallic layer in accordance with step E),-   G) optionally, treating the metallic substrate obtained according to    step A) or D), or treating the coatable surface of the metallic    substrate obtained according to step A) or D) or of the metallic    layer obtained according to step E) or F) with at least one    organosilicon compound, in particular by use of plasma    polymerization, thus forming a polysiloxane layer,-   H) optionally, plasma treatment with the plasma generator and/or    corona treatment of the polysiloxane layer in accordance with step    G),-   I) optionally, applying a conversion layer onto the metallic    substrate or the coatable surface of the metallic substrate in    accordance with step A) or D), or onto the metallic layer in    accordance with step E) or F), or onto the polysiloxane layer in    accordance with step G) or H),-   J) optionally, plasma treatment with the plasma generator and/or    corona treatment of the conversion layer in accordance with step I),-   K) optionally, treating the conversion layer obtained according to    step I) or J) with at least one organosilicon compound, in    particular by use of plasma polymerization, thus forming a    polysiloxane layer,-   L) optionally, plasma treatment with the plasma generator and/or    corona treatment of the treated polysiloxane layer obtained    according to step K),-   M) optionally, applying at least one, optionally coloured, primer    layer onto the metallic substrate or the coatable surface of the    metallic substrate in accordance with step A) or D), or onto the    metallic layer in accordance with step E) or F), or onto the    polysiloxane layer in accordance with step G) or H), or onto the    conversion layer in accordance with step I) or J), or onto the    polysiloxane layer in accordance with step K) or L),-   N) optionally, plasma treatment with the plasma generator and/or    corona treatment of the primer layer in accordance with step M),-   O) optionally, treating the primer layer obtained according to    step M) or N) with least one organosilicon compound, in particular    by use of plasma polymerization, thus forming a polysiloxane layer,-   P) optionally, plasma treatment with the plasma generator and/or    corona treatment of the treated polysiloxane layer obtained    according to step 0),-   P-Q) applying at least one matt, in particular colour, coating, such    as a matt lacquer, in particular with gloss grade “medium gloss”    (G2) or preferably with gloss grade “matt” (G3), respectively    determined according to DIN EN ISO 2813:2014 (issue date: 2015-02)    or applying at least one gloss, in particular colour, coating, such    as a gloss lacquer, in particular with gloss grade “glossy” (G1),    determined according to DIN EN ISO 2813:2014 (issue date: 2015-02),    preferably applying the matt coating,-   Q) applying at least one metallic layer, containing or consisting of    a first metal, selected from the group consisting of aluminium,    silver, gold, lead, vanadium, manganese, magnesium, iron, cobalt,    molybdenum, tungsten, nickel, copper, chromium, palladium, platinum,    titanium, zirconium and zinc, in particular aluminium, or containing    or consisting of a first metal alloy, selected from the group    consisting of brass, bronze, steel, in particular special steel or    stainless steel, alloys of aluminium, magnesium and titanium, with    the application system, in particular by use of vapour deposition    and/or sputtering technology, onto the primer layer in accordance    with step P-Q),-   R) optionally, plasma treatment with the plasma generator and/or    corona treatment of the metallic layer in accordance with step Q),-   S) preferably treating the metallic layer obtained according to    step Q) or R) with at least one organosilicon compound, in    particular by use of plasma polymerization, thus forming a    polysiloxane layer,-   T) preferably plasma treatment with the plasma generator and/or    corona treatment of the polysiloxane layer in accordance with step    S), and-   U) applying at least one, in particular transparent and/or coloured,    overcoat onto the layer in accordance with steps Q), R), S) or T),    in particular onto the treated polysiloxane layer in accordance with    step T).

With the method described, the metallic layer, in particular thealuminium layer, is preferably applied in step Q) in a thickness, inparticular vapour deposited or sputtered on, so that the metallic layer,in particular also in accordance with steps l), m), n), and/or o), isnot transparent and not translucent for visible light. It hassurprisingly been shown that although the metallic layer is applied in athickness that is not translucent or even not transparent for visiblelight, the final product obtained according to this method neverthelessprovides a matt appearance. The matt character is accordinglytransferred to the applied metallic layer. As a result, the non-metallicsubstrate obtains according to this method, in particular coated plasticproducts, are given a very elegant appearance. Here, it is alsoadvantageous that they not only stand out for a high degree of corrosionprotection, but also, as is otherwise frequently the case among productswith matt surfaces, mechanical influences on the surface do not impairthe appearance of this surface. For example, no abrasion or no change tothe matt appearance is observed in the places where mechanical influencewas made. In a corresponding manner, through the use of a glossycoating, the gloss of the metallic layer applied over it can again beintensified. Any colours required can be used for the creation of a mattor glossy coating. If the metallic layer is applied opaquely, in otherwords such that it is not transparent for visible light and also nottranslucent, only the matt or glossy character of the coating istransferred onto the applied metallic layer, but not also the colour ofthis coating. Persons skilled in the art are familiar with matt andglossy coatings. Matt coatings can for example be obtained using aso-called matting paste.

With the method described above, in a preferred embodiment, steps S) andT) are conducted prior to step U).

The object on which the invention is based is further achieved by amethod for manufacturing a coated metallic substrate, comprising

-   A) provision of a metallic substrate with at least one surface which    is capable of being coated at least in part areas,-   B) provision of an application system for the application of a    metallic layer, in particular a vacuum vapour deposition system,-   C) provision of at least one plasma generator and/or at least one    corona system, in particular within the application system for the    application of a metallic layer, such as the vacuum vapour    deposition system or the sputtering system, or as a component    thereof,-   D) optionally, cleaning of the metallic substrate or of the coatable    surface of the metallic substrate,-   E) optionally, applying at least one metallic layer, containing or    consisting of a second metal, selected from the group consisting of    titanium, hafnium and zirconium, in particular zirconium, or of a    second metal alloy, selected from the group consisting of alloys of    titanium, hafnium and zirconium, with the application system, in    particular by use of vapour deposition and/or sputtering technology,    onto the metallic substrate or the coatable surface of the metallic    substrate in accordance with step A) or D),-   F) optionally, plasma treatment with the plasma generator and/or    corona treatment of the metallic substrate or of the coatable    surface of the metallic substrate in accordance with step A) or D),    or of the metallic layer in accordance with step E),-   G) optionally, treating the metallic substrate obtained according to    step A) or D), or treating the coatable surface of the metallic    substrate obtained according to step A) or D) or of the metallic    layer obtained according to step E) or F) with at least one    organosilicon compound, in particular by use of plasma    polymerization, thus forming a polysiloxane layer,-   H) optionally, plasma treatment with the plasma generator and/or    corona treatment of the polysiloxane layer in accordance with step    G),-   I) optionally, applying a conversion layer onto the metallic    substrate or the coatable surface of the metallic substrate in    accordance with step A) or D), or onto the metallic layer in    accordance with step E) or F), or onto the polysiloxane layer in    accordance with step G) or H),-   J) optionally, plasma treatment with the plasma generator and/or    corona treatment of the conversion layer in accordance with step I),-   K) optionally, treating the conversion layer obtained according to    step I) or J) with at least one organosilicon compound, in    particular by use of plasma polymerization, thus forming a    polysiloxane layer,-   L) optionally, plasma treatment with the plasma generator and/or    corona treatment of the treated polysiloxane layer obtained    according to step K),-   M) optionally, applying at least one, preferably coloured, primer    layer onto the metallic substrate or the coatable surface of the    metallic substrate in accordance with step A) or D), or onto the    metallic layer in accordance with step E) or F), or onto the    polysiloxane layer in accordance with step G) or H), or onto the    conversion layer in accordance with step I) or J), or onto the    polysiloxane layer in accordance with step K) or L),-   N) optionally, plasma treatment with the plasma generator and/or    corona treatment of the primer layer in accordance with step M),-   O) optionally, treating the primer layer obtained according to    step M) or N) with least one organosilicon compound, in particular    by use of plasma polymerization, thus forming a polysiloxane layer,-   P) optionally, plasma treatment with the plasma generator and/or    corona treatment of the treated polysiloxane layer obtained    according to step O),-   PP-QQ) preferably, applying at least one colour layer onto the    metallic substrate or the coatable surface of the metallic substrate    in accordance with step A) or D), or onto the metallic layer in    accordance with step E) or F), or onto the polysiloxane layer in    accordance with step G) or H), or onto the conversion layer in    accordance with step I) or J), or onto the polysiloxane layer in    accordance with step K) or L), or onto the primer layer according to    step M) or N), or onto the polysiloxane layer according to step O)    or P),-   Q′) applying at least one metallic layer, containing or consisting    of one first metal selected from the group consisting of aluminium,    silver, gold, lead, vanadium, manganese, magnesium, iron, cobalt,    nickel, copper, chromium, palladium, platinum, titanium, zirconium    and zinc, in particular aluminium, or containing or consisting of a    first metal alloy, selected from the group consisting of brass,    bronze, steel, in particular special steel or stainless steel,    alloys of aluminium, magnesium and titanium, with the application    system, in particular by use of vapour deposition and/or sputtering    technology, onto the metallic substrate or the coatable surface of    the metallic substrate in accordance with step A) or D), or onto the    metallic layer in accordance with step E) or F), or onto the    polysiloxane layer in accordance with step G) or H), or onto the    conversion layer in accordance with step I) or J), or onto the    polysiloxane layer in accordance with step K) or L), or onto the    primer layer in accordance with step M) or N), or onto the    polysiloxane layer in accordance with step O) or P), or onto the    colour layer in accordance with PP-QQ), whereby the metallic layer,    in particular the aluminium layer, is applied in a thickness, in    particular by use of vapour deposition or sputtering technology,    such that the metallic layer, in particular also according to step    l), m), n) and/or o), is transparent or translucent for visible    light,-   R) optionally, plasma treatment with the plasma generator and/or    corona treatment of the metallic layer in accordance with step Q′),-   S) preferably treating the metallic layer obtained according to    step Q) or R) with at least one organosilicon compound, in    particular by use of plasma polymerization, thus forming a    polysiloxane layer,-   T) preferably plasma treatment with the plasma generator and/or    corona treatment of the polysiloxane layer in accordance with step    S), and-   U) applying at least one, in particular transparent and/or coloured,    overcoat onto the layer in accordance with steps Q′), R), S) or T),    in particular onto the treated polysiloxane layer in accordance with    step T).

The transparent or translucent metallic layer in step Q′) herepreferably has an average, in particular absolute, thickness in therange of 1 nm to 50 nm, preferably in the range of 10 nm to 40 nm, andparticularly preferred in the range of 15 nm to 30 nm.

With the method described above, in a preferred embodiment, steps S) andT) are conducted prior to step U).

Adjacent to the transparent or translucent metallic layer (layer Q′), onthe other side of the overcoat, preferably, the colour layer (layerPP-QQ), the colour or coloured polysiloxane layer, the colour orcoloured primer layer or the colour or coloured non-metallic substrateare placed. In this manner, very high-quality appearance coating systemsare obtained. For example, through the use of a black colour layer or ablack coloured primer layer, which are placed on the transparent ortranslucent metallic layer, the impression of a black chromium layer canbe created.

With the method described above for coating non-metallic substrates, inparticular plastic substrates, those method variants have been shown tobe advantageous, in particular for obtaining highly satisfactory resultswith regard to adhesion, gloss and/or corrosion resistance, in which

steps D), M), N), P-Q), Q), S), T) and U) or D), M), N), Q′), S), T) andU) or D), M), N), PP-QQ), Q′), S), T) and U) respectively, in particulardirectly, follow each other, or

steps D), M), N), P-Q), Q), S), T) and U) or D), M), N), O), Q′), S), T)and U) or D), M), N), O), PP-QQ), Q′), S), T) and U) respectively, inparticular directly, follow each other, or

steps D), E), F,), M), P-Q), Q), S), T) and U) or D), E), F), M), Q′),S), T) and U) or D), E), F,), M), PP-QQ), Q′), S), T) and U)respectively, in particular directly, follow each other, or

steps D), E), F,), M), O), P-Q), Q), S), T) and U) or D), E), F,), M),O), Q′), S), T) and U) or D), E), F,), M), O), PP-QQ), Q′), S), T) andU) respectively, in particular directly, follow each other, or

steps D), G), H), M), P-Q), Q), S), T) and U) or D), G), H), M), Q′),S), T) and U) or D), G), H), M), PP-QQ), Q′), S), T) and U)respectively, in particular directly, follow each other, or

steps D), O), H), M), O), P-Q), Q), S), T) and U) or D), G), H), M), O),Q′), S), T) and U) or D), G), H), M), O), PP-QQ), Q′), S), T) and U)respectively, in particular directly, follow each other, or

steps D), E), G), H), M), P-Q), Q), S), T) and U) or D), E), G), H), M),Q′), S), T) and U) or D), E), G), H), M), PP-QQ), Q′), S), T) and U)respectively, in particular directly, follow each other, or

steps D), E), G), H), M), O), P-Q), Q), S), T) and U) or D), E), G), H),M), O), Q′), S), T) and U) or D), E), G), H), M), O), PP-QQ), Q′), S),T) and U) respectively, in particular directly, follow each other, or

steps D), M), P-Q), Q), S), T) and U) or D), M), Q′), S), T) and U) orD), M), PP-QQ), Q′), S), T) and U) respectively, in particular directly,follow each other, or steps D), M), O), P-Q), Q), S), T) and U) or D),M), O), Q′), S), T) and U) or D), M), O), PP-QQ), Q′), S), T) and U)respectively, in particular directly, follow each other, or

steps D), G), H), P-Q), Q), S), T) and U) or D), G), H), Q′), S), T) andU) or D), G), H), PP-QQ), Q′), S), T) and U) respectively, in particulardirectly, follow each other, or

steps D), G), H), O), P-Q), Q), S), T) and U) or D), G), H), O), Q′),S), T) and U) or D), G), H), PP-QQ), O), Q′), S), T) and U)respectively, in particular directly, follow each other.

It has shown for some applications that it is also of advantage in themanufacture of coated metallic substrates if a polysiloxane layer, inparticular a plasma-polymerized polysiloxane layer, is present on bothsides of the metallic layer, i.e. method step O) is interspersed,preferably with subsequent plasma treatment and/or corona treatment, inparticular plasma treatment. It is therefore possible, for example, forthe method variant described heretofore also to be provided with stepO).

A particularly significant corrosion protection is also obtained withthe metallic substrate which is obtainable in accordance with the methodaccording to the invention, if at least one metallic layer is appliedonto the metallic substrate cleaned in accordance with step D), or ontothe cleaned coatable surface of the metallic substrate, this metalliclayer containing or consisting of a second metal, selected from thegroup consisting of titanium, hafnium and zirconium, in particularzirconium, or of a second metal alloy, selected from the groupconsisting of alloys of titanium, hafnium and zirconium, with theapplication system, in particular by use of vapour deposition and/orsputtering technology (step E)). It is particularly advantageous if thismetallic layer is subsequently subjected to a plasma treatment step(step F)).

In one particularly purposeful embodiment, the layer onto which themetallic layer is applied in accordance with step Q) or Q′) is subjectedto a plasma treatment with the plasma generator and/or a coronatreatment (for example, steps P), N), L), J), H), F) or D)) before thestep Q) or Q′). This also applies, in particular, to the polysiloxanelayer.

It has also proved advantageous, in a preferred embodiment, inparticular in relation to good adherence and corrosion protection, ifthe metallic substrate, in particular the cleaned metallic substrate, issubjected to a plasma treatment and/or a corona treatment, in particulara plasma treatment (step F)).

In many cases, it has therefore proved advantageous if a polysiloxanelayer is applied, this layer is then subjected to a plasma treatmentand/or a corona treatment, in particular a plasma treatment. The sameapplies to the application of a primer layer. Here, too, it has provedadvantageous when the primer layer obtained is first subjected to aplasma treatment and/or a corona treatment, in particular a plasmatreatment.

It has accordingly also proved advantageous in the manufacture of coatedmetallic substrates according to the inventive method if the methodsteps referred to heretofore are carried out essentially immediatelyfollowing one another. This means, in particular, that an extended dwellperiod after the plasma treatment steps should be avoided. Rather, it isof advantage if the subsequent method step follows directly. It has alsoshown that it is not necessary for further method steps to beinterspersed between the method steps referred to heretofore.

For the metallic substrates, recourse can be made to metals and metalalloys, wherein particularly suitable metallic substrates can beselected from the group consisting of aluminium, aluminium alloys, iron,iron alloys, in particular steel or special or stainless steel, copper,copper alloys, titanium, titanium alloys. zinc, zinc alloys, nickel,nickel alloys, molybdenum, molybdenum alloys, magnesium, magnesiumalloys, lead, lead alloys, tungsten, tungsten alloys, manganese,manganese alloys, brass, bronze, die-cast nickel, diecast zinc anddie-cast aluminium, or any mixtures thereof.

Suitable methods for cleaning metallic substrates are known to theperson skilled in the art. Such cleaning methods (step D)) comprisedegreasing, pickling, phosphating, in particular iron phosphating and/orzinc phosphating, polishing, grinding, in particular finish grinding,and/or treating with dry ice. These methods can be used bothindividually as well as in any desired combination. For manyapplications it had proved sufficient for the metallic substrates to becleaned by treating them with dry ice. During cleaning with dry ice, ingeneral, dry ice particles in the form of pellets or in the form ofcrystals, which have been shaved off an appropriate block of dry ice,are accelerated with the aid of compressed air and directed onto themetallic surface which is to be cleaned. The cleaning effect is assumedto be attributable to thermal, kinetic, and phase transformationeffects. Devices and methods for the cleaning of metallic surfaces withdry ice can be found, for example, in DE 195 44 906 A1 and EP 2 886 250.

The surface of metallic substrates can be degreased, for example, withalkaline or acidic reagents. Commercial degreasing steps are also knownunder the terms of hot alkaline cleaning or pickling cleaning. As analternative, a metallic surface can be degreased by anode effect in anelectrolytic degreasing bath.

For a number of variant embodiments it is advantageous for the metallicsubstrate surface, in particular the degreased metallic substratesurface, to be subjected to at least one pickling step. For pickling themetallic substrate surface, use is made, for example, of an acidicflushing bath. A suitable pickling solution is provided, for example, bydilute hydrochloric acid (1:10 vol/vol). As a result of pickling, as arule, a metallic surface is obtained which is essentially free ofoxides. Like the degreasing step, the pickling step is, in general,concluded by a flushing step. If the metallic substrate surface ispolished and/or ground or finish-ground, it is frequently possible to dowithout the degreasing step and/or pickling step. With this form ofsurface treatment, sufficient material is usually removed from thissurface for any contamination or other constituents adhering to thesurface to be removed together with it. If the surface is polished orground, it is frequently also possible to omit the application of afirst and, optionally, second primer layer. In most cases, polishing orgrinding already provides a surface which is sufficiently flat or smoothfor further smoothing by the application of a primer layer to be nolonger necessary. It may, however, be recommendable for a first andpossibly also a second primer step to be added if the metallic substratehas a considerable number of angles and corners, which cannot simply beadequately polished or ground without further ado.

Following or instead of the degreasing step, the metallic substratesurface can be phosphated and/or passivated. This is preferred, inparticular, with substrates made of or containing aluminium.

In a further embodiment of the method according to the invention formanufacturing coated metallic substrates, substrates with veryparticular corrosion resistance can be attained if, in the step of theapplication of the metallic layer, a first metal, in particularaluminium, or a first metal alloy, in particular an aluminium alloy, isco-vapour deposited in the application system for the application of ametallic layer, in particular the vacuum vapour deposition system or thesputtering system, overlapping in time with a second metal, which isdifferent from the first metal, in particular selected from the groupconsisting of titanium, zirconium and hafnium, in particular zirconium,or with a second metal alloy, in particular a zirconium alloy, which isdifferent from the first metal alloy. This takes place, for example, inthe form that metal pellets or rods of the first metal or the firstmetal alloy are introduced into an appropriate first receptioncontainer, in particular a first boat element or a first helical shaft,and the metal pellets or rods of the second metal or the second metalalloy are introduced into an appropriate second reception container,second boat element or a second helical shaft, and that the first andthe second reception container are heated in such a way that the meltingpoints of the first and second metals or of the first and second metalalloys or of the first metal and second metal alloy or of the firstmetal alloy and second metal are attained and/or maintained essentiallysimultaneously or within an overlapping period of time.

Suitable aqueous conversion systems, with the aid of which conversionlayers are obtained, are familiar to the person skilled in the art. Byway of example, reference may be made to the disclosures of U.S. Pat.No. 2,825,697 and U.S. Pat. No. 2,928,763.

For the application of the primer layer, generally known methods are atthe disposal of the person skilled in the art. Accordingly, in apreferred embodiment, the primer layer may be based in particular onUV-curing powdery polyester resin compounds or to epoxy/polyesterpowder. Examples which may be referred to include the wet-coatingprocess, the powder-coating process, or application by use of UV-curingcoating systems. It is, of course, also possible, to carry out amechanical smoothing of the metallic substrate surface, for example bygrinding and/or polishing or finish-grinding, before the application ofa primer layer, as described heretofore.

Suitable organosilicon compounds are known to the person skilled in art.In one purposeful embodiment, recourse is made for this purpose to atleast one amino-containing silane, in particularaminopropyltriethoxysilane, hexamethyldisiloxane, tetramethyldisiloxane,or any mixtures thereof. It is particularly preferred that use is madeof hexamethyldisiloxane and tetramethyldisiloxane, whereinhexamethyldisiloxane is regularly particularly well-suited.

Suitable organosilicon compounds likewise comprise, as monomer or asco-monomer structural units, compounds of the following formula (I):

X-R_(j)-Si(R₂)_(3-m)(R₃)_(m)   (I),

wherein the substituents and indices have the following meaning:

-   m 0, 1, 2 or 3, in particular 2 or 3,-   R1 C1 to C10 hydrocarbon residue, in particular a C1 to C10    hydrocarbon chain, which may be interrupted by oxygen or nitrogen,    in particular methyl, ethyl, or i- or n-propyl, preferably i- or    n-propyl,-   R2 identical or different hydrolysable groups, in particular alkoxy    groups, such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy,    i-butoxy or t-butoxy, in particular methoxy or ethoxy,-   R3 identical or different C1 to C5 alkyl groups, in particular    methyl, ethyl or i- or n-propyl, preferably i- or n-propyl,-   X functional polymerisable group, in particular an unsaturated    organic residue in the ω position, such as an unsaturated alkenyl    group in the ω position with 1 to 10, preferably 2 to 4 C atoms, or    an unsaturated carboxylic acid residue in the ω position of    carboxylic acids with up to 4 carbon atoms, and alcohols with up to    6 carbon atoms.

Particularly suitable residues X comprise, for example, vinyl,alkylvinyl, in particular methyl, ethyl or propyl vinyl,(meth)acryloxyalkyl, in particular (meth)acryloxymethyl,(meth)acryloxyethylene or (meth)acryloxypropyl, in particular(meth)acryloxypropyl.

In a further development of the method according to the invention,provision is made for a first organosilicon compound to be delivered tothe application system, in particular vacuum chamber, via a feed linefrom a first container located outside the application system for theapplication of a metallic layer, in particular outside the vacuumchamber of the vacuum vapour deposition system, and for a secondorganosilicon compound, which is different from the first organosiliconcompound, to be delivered to the application system, in particularvacuum chamber, via a feed line from a second container located outsidethe application system for the application of a metallic layer, inparticular outside the vacuum chamber of the vacuum vapour depositionsystem. As an alternative, the same organosilicon compound can bepresent in the first and second container. In particular, it ispossible, that, if the same organosilicon compounds are used, one ofthese organosilicon compounds can be present mixed with a further,different organosilicon compound and/or with a colouring agent, inparticular a dye. Accordingly, the methods according to the inventionare also characterized in that, together with the at least oneorganosilicon compound, in particular for the plasma polymerization, atleast one colouring agent, in particular a dye, is introduced into theapplication system for the application of a metallic layer, preferablyin the form of a mixture. This latter method variant, comprising the useof a colouring agent, naturally is also successful if only one containeris used.

An application system suitable for the implementation of the methodaccording to the invention, for the application of a metallic layer,comprising at least one first container, located in particular outsidethe application system for the application of a metallic layer, inparticular outside the vacuum chamber of the vacuum vapour depositionsystem, for holding a first organosilicon compound, with a feed line tothe application system, in particular to the vacuum chamber, and atleast one second container, located in particular outside theapplication system for the application of a metallic layer, inparticular outside the vacuum chamber of the vacuum vapour depositionsystem, for holding a second organosilicon compound, with a feed line tothe application system, in particular to the vacuum chamber.

Particularly good adherence without restrictions with regard tocorrosion resistance is also achieved in particular due to the fact thatthe step of treatment with at least one organosilicon compound, such ashexamethyldisiloxane, in particular by use of plasma polymerization,thus forming a polysiloxane layer, takes place in the presence of atleast one reactive gas, such as oxygen, nitrogen, carbon dioxide,hydrogen, carbon monoxide, hydrogen peroxide gas, water vapour, ozoneand/or air, in particular in the presence of oxygen or air. By way ofthe integration of reactive gases, in particular air or oxygen, into thepolymerization process, in particular plasma-generated, harderpolysiloxane layers are obtained than with the conventional manufactureof such polysiloxane layers, without the concomitant use of the reactivegases described. These harder polysiloxane layers are also characterizedby greater diffusion consistency. In this context, in a particularlypurposeful embodiment, provision can be made for the at least oneorganosilicon compound, in particular hexamethyldisiloxane, and the atleast one reactive gas, in particular oxygen or air, to be used as amixture for the treatment step. The embodiment described heretofore ofthe concomitant use of reactive gases in the production, in particularplasmagenerated, of the polysiloxane layer, is used preferably in atleast one step of the treatment with at least one organosiliconcompound, in particular by use of plasma polymerization, thus forming apolysiloxane layer, or also with each step for the production of apolysiloxane layer. It is particularly preferred that this methodvariant is used in the manufacture of coated non-metallic substrates, inparticular of plastic substrates, in method step m) and in themanufacture of coated metallic substrates in method step S). In themethod steps following those referred to, namely method steps n) and T)respectively, the plasma treatment is preferably carried out with theaid of a plasma gas, formed from an inert gas, in particular argon, andoxygen or air or nitrogen, in particular oxygen, or with the aid of aplasma gas formed from oxygen, air or nitrogen. This procedure againcontributes to a better adherence of the total system, including theovercoat.

For the step of the plasma treatment with the plasma generator, thereare in principle a number of method variants available for selection.According to a first variant, the plasma can be formed using at leastone inert gas, in particular argon. As an alternative, for thegeneration of a suitable plasma, recourse can also be made to mixturesof at least one inert gas, in particular argon, and a reactive gas suchas oxygen, nitrogen, carbon dioxide, hydrogen, carbon monoxide, hydrogenperoxide gas, water vapour, ozone and/or air. Use is made herepreferably of oxygen and nitrogen, in particular oxygen. Finally, it isalso possible to exclude inert gases and to use exclusively reactivegases, such as oxygen, nitrogen, hydrogen, carbon dioxide, carbonmonoxide, hydrogen peroxide gas, water vapour, ozone and/or air for theproduction of the plasma. In this situation, recourse is made preferablyto oxygen. With the aid of a plasma treatment with the plasma generator,the surface to be coated of the substrate is activated. In a plasmaprocess, an energy-rich plasma regularly takes effect on the surface ofthe shaped part such that active centres are formed on this surface.This can involve, for example, hydroxyl groups and/or carbonyl groups.In the same way, an activation of the surface of the substrate surfacewhich is to be coated can be put into effect by flame treatment. In apreferred embodiment, a volatile silane or a compound containingtitanium and aluminium can be added to a flame, such as a propane gasflame, which burns in an air atmosphere. Due to the flame application,the surface of the substrate, in particular of a plastic substrate, canbe changed in a similar manner as in the plasma process, thus forminghydroxyl groups, for example.

The methods according to the invention provide the great advantage thatalmost all method steps can be carried out in the application system forthe application of a metallic layer. As well as the application of themetallic layers, this also relates to the activation of surfaces by useof the plasma treatment with the plasma generator, as well as to theapplication of the polysiloxane layer, in particular by use of plasmapolymerization. Only the cleaning step, the application of a primerlayer, the application of a conversion layer, and the application of theovercoat are regularly carried out outside the application systemreferred to. Provision can therefore be made that the plasma treatment,in particular each plasma treatment, is carried out with the plasmagenerator and/or the application, in particular each application, of themetallic layer, and/or the application, in particular each application,of the polysiloxane layer is carried out within the application systemfor the application of a metallic layer, in particular in the vacuumvapour deposition system or in the sputtering system, and/or that theapplication of the primer layer and/or the application of the conversionlayer and/or the application of the overcoat takes place outside theapplication system for the application of a metallic layer, inparticular of the vacuum vapour deposition system or of the sputteringsystem.

For the overcoat, for example, recourse can also be made towater-dilutable coating compositions. The overcoat can be formed frompolyacrylate resins, polyester resins, aminoplast resins, orpolyurethane compounds. Preferably, in the methods according to theinvention, such overcoats are applied as are based on a UV-curingcoating material. Accordingly, a preferred overcoat is a UV-curedovercoat. The overcoat can be obtained, for example, by use of a clearlacquer or a transparent powder. The overcoat is preferably applied by awet-lacquer process or a powder coating process. The overcoat canaccordingly be, for example, a single-component, two-component, ormulti-component lacquer, wherein clear lacquers are preferred. Theseclear lacquers can be, for example, chemically cross-linkingtwo-component lacquers, single-component heat-curing lacquers, orUV-curing lacquers. In addition, 1K or 2K stoving lacquer can be usedfor the overcoat.

As a rule, the overcoat has a thickness in the range from 10 to 50 μm,preferably in the range from 20 to 30 μm. Of inventive importance to themethod according to the invention is the fact that the material formingthe overcoat is applied onto a polysiloxane layer which has beenpreviously activated by use of plasma treatment and/or corona treatmentand which was preferably obtained by a plasma polymerization, andpreferably essentially without any time delay.

The plasma treatment with the plasma generator is sometimes alsodescribed by the term glowing.

For the application of the metallic layers, recourse can be made, forexample, to the technologies of Physical Vapor Deposition (PVD),Chemical Vapor Deposition (CVD), vapour deposition by use of an electronbeam evaporator, vapour deposition by use of a resistance evaporator,induction vapour deposition, ARC evaporation, or cathode or anodeatomization (sputter coating). Accordingly, application systems for theapplication of a metallic layer preferably include, for example, vacuumvapour deposition systems or sputtering systems. Suitable vacuum vapourdeposition systems purposefully comprise PVD systems (Physical VaporDeposition), CVD systems (Chemical Vapor Deposition), electron beamevaporators, resistance evaporators, induction evaporators, and ARCevaporators. Suitable sputtering systems comprise, for example, cathodeatomizers and anode atomizers. As the person skilled in the art knows, ametallic layer consists predominantly of metal. This does not entirelyexclude additives, such as are used, for example, with stainless steelin the form of carbon. Preferably, the metal content of the metalliclayer in this situation is greater than 90% by weight, in particular 95%by weight, and more particularly 98% by weight.

Preferably, the metallic layer is a vapour-deposited or sputter-appliedmetallic layer, in particular a PVD metallic layer. In the PVD method,in general, resistance-heated metal helical shaft or metal boat elementevaporators are used, wherein tungsten chutes of the most widelydiffering forms are preferred. In the PVD method, in general, anevaporator is fitted with helical shafts which can be clamped ontoevaporator rails which are insulated from one another. Preferably, aprecisely determined quantity of metal to be deposited is introducedinto each chute. After the PVD system has been closed and evacuated, theevaporation can be started by switching on the power supply, as a resultof which the evaporation rails cause the chutes to be brought to a glow.The solid metal begins to melt, and thoroughly wets the chutes, which inmost cases are twisted in form. By the further application of energy,the liquid metal is transformed into the gas phase, so that it can thenbe deposited on the substrate which is to be coated. By way of thequantity of metal transformed into the gas phase, and/or the duration ofthe coating phase, the thickness of the metallic layer, and thereforealso its appearance, can be specifically adjusted.

A further preferred method for depositing the metallic layer onto thesubstrate is cathode atomization (sputtering). Here, a cathode isarranged in an evacuated container and connected to the negative pole ofa current supply. The coating material which is to be atomized isarranged directly in front of the cathode, and the substrates which areto be coated are arranged opposite the coating material which is to beatomized. In addition, argon can be conveyed, as the process gas,through the container, which also comprises an anode which is connectedto the positive pole of a current supply. Once the container has beenpre-evacuated, the cathode and anode are connected to the currentsupply. Due to the targeted and controlled intake of argon, the averagefree path length of the charge carriers is significantly reduced. Argonatoms are ionised in the electrical field between the cathode and anode.The positively charged particles are accelerated with high energytowards the negatively charged cathode. On impinging, and due toparticle impacts in the coating material, this material is transformedinto the vapour phase, accelerates with high energy into the free space,and then condenses on the substrates which are to be coated. Sputteringallows for different metallic layer thicknesses to be specificallyadjusted.

A colouring of the coating present on the non-metallic and metallicsubstrates can also be accomplished with the methods according to theinvention, if a coating material is used for the application of theovercoat which contains at least one colouring agent, e.g. at least onepigment and/or at least one dye. Glazes, which are known to the personskilled in the art, can also be used in order to colour the overcoat,such as to obtain, for example, brass, titanium and gold colour shades,or individual colour shades such as red, blue, yellow, green, etc., oranodized colour shades. For example, effect pigments can also beintroduced into the overcoat, such as pearl gloss pigments, LCP (liquidcrystal polymer) pigments or OV (optical variable) pigments.

The object that forms the basis of the invention is further attained bya coated, non-metallic substrate, in particular a coated plasticsubstrate, preferably obtained or obtainable according to a methodaccording to the invention, comprising, in this order,

-   -   a, in particular plasma and/or corona-treated, non-metallic        substrate, in particular a plastic substrate;    -   optionally, a polysiloxane layer, in particular obtained by use        of plasma polymerisation of at least one organosilicon compound,        which is preferably plasma and/or corona-treated;    -   optionally, at least one, preferably plasma and/or        corona-treated and/or coloured primer layer;    -   optionally, a polysiloxane layer, in particular obtained by use        of plasma polymerisation of at least one organosilicon compound,        which is preferably plasma and/or corona-treated,    -   at least one matt, in particular colour, coating, such as a matt        paint, in particular with gloss grade “medium gloss” (G2) or        preferably with gloss grade “matt” (G3), respectively determined        according to DIN EN ISO 2813:2014 (issue date: 2015-02) or at        least one gloss, in particular colour, coating, such as a gloss        paint, in particular with gloss grade “glossy” (G1), determined        according to DIN EN ISO 2813:2014 (issue date: 2015-02),        preferably the matt coating;    -   a metallic layer obtained using vapour deposition and/or        sputtering technology, preferably plasma and/or corona-treated,        containing or consisting of a first metal, selected from the        group consisting of aluminium, silver, gold, lead, vanadium,        manganese, magnesium, iron, cobalt, molybdenum, tungsten,        nickel, copper, chromium, palladium, platinum, titanium,        zirconium and zinc, in particular aluminium, or containing or        consisting of a first metal alloy, selected from the group        consisting of brass, bronze, steel, in particular special steel        or stainless steel, alloys of aluminium, magnesium and titanium,        in particular an aluminium layer;    -   preferably a polysiloxane layer, in particular obtained by use        of plasma polymerisation of at least one organosilicon compound,        which is preferably plasma and/or corona-treated,    -   at least one, in particular transparent and/or coloured,        overcoat, preferably on the treated polysiloxane layer.

The metallic layer advantageously has a thickness that is nottransparent and not translucent for visible light. Such a metallic layercan also be described as opaque. A metallic layer is not transparent inthe sense of the present invention when, applied onto the substrate oronto a layer present on the substrate, details of the substrate or thelayer are not recognisable, i.e. the metallic layer is not visionpermeable. A metallic layer is not translucent in the sense of thepresent invention when, applied onto the substrate or onto a layerpresent on the substrate, details of the substrate or the layer are notrecognisable, i.e. the metallic layer is not light impermeable. In otherwords, a translucent metallic layer is light permeable, but not visionpermeable. With a translucent metallic layer, e.g. the colour of thesubstrate or the coating lying underneath can be recognised.

The object that forms the basis of the invention is further attained bya coated, non-metallic substrate, in particular a coated plasticsubstrate, preferably obtained or obtainable according to a methodaccording to the invention, comprising, in this order,

-   -   a, in particular plasma and/or corona-treated, non-metallic        substrate, in particular a plastic substrate;    -   optionally, a polysiloxane layer, in particular obtained by use        of plasma polymerisation of at least one organosilicon compound,        which is preferably plasma and/or corona-treated;    -   optionally, at least one, preferably plasma and/or        corona-treated, in particular a coloured, primer layer;    -   optionally, a polysiloxane layer, in particular obtained by use        of plasma polymerisation of at least one organosilicon compound,        which is preferably plasma and/or corona-treated,    -   preferably, at least one, preferably plasma and/or        corona-treated, colour layer; a metallic layer obtained by use        of vapour deposition and/or sputtering technology, preferably        plasma and/or corona-treated, containing or consisting of a        first metal, selected from the group consisting of aluminium,        silver, gold, lead, vanadium, manganese, magnesium, iron,        cobalt, molybdenum, tungsten, nickel, copper, chromium,        palladium, platinum, titanium, zirconium and zinc, in particular        aluminium, or containing or consisting of a first metal alloy,        selected from the group consisting of brass, bronze, steel, in        particular special steel or stainless steel, alloys of        aluminium, magnesium and titanium, with the application system,        in particular an aluminium layer, which is transparent or        translucent for visible light;    -   preferably a polysiloxane layer, in particular obtained by use        of plasma polymerisation of at least one organosilicon compound,        which is preferably plasma and/or corona-treated,    -   at least one, in particular transparent and/or coloured,        overcoat, preferably on the treated polysiloxane layer.

The transparent or translucent metallic layer advantageously has anaverage, in particular absolute, thickness in the range of 1 nm to 50nm, preferably in the range of 10 nm to 40 nm, and particularlypreferred in the range of 15 nm to 30 nm.

With the coated non-metallic substrate described above, such anembodiment is preferred in which a polysiloxane layer is present betweenthe metallic layer and the coating layer which is obtained by use ofplasma polymerisation of at least one organosilicon compound, which hasalso been plasma and/or corona-treated.

Additionally, such an embodiment variant is preferred in which adjacentto the metallic layer obtained by use of the vapour deposition and/orsputtering technology, the colour layer, the colour or colouredpolysiloxane layer, the colour or coloured primer layer of the colour orcoloured non-metallic substrate is present.

Particularly attractive, in particular elegant, surfaces can here alsobe achieved in that the non-metallic substrate, at least onepolysiloxane layer, the primer layer, the matt or glossy coat, thecolour layer, the metallic layer and/or the coating layer, in particularthe matt or glossy coating or the colour layer, have a structuredsurface.

The object that forms the basis of the invention is further attained bya coated metallic substrate, in particular obtained or obtainableaccording to a method according to the invention, comprising, in thisorder,

-   -   a, in particular plasma and/or corona-treated and/or purified,        metallic substrate;    -   optionally, a metallic layer obtained by use of vapour        deposition and/or sputtering technology, which is preferably        plasma and/or corona-treated, containing or consisting of a        second metal selected from the group consisting of titanium,        hafnium and zirconium, in particular zirconium, or selected from        a second metal alloy from the group consisting of titanium,        hafnium and zirconium alloys;    -   optionally, a polysiloxane layer, in particular obtained by use        of plasma polymerisation of at least one organosilicon compound,        which is preferably plasma and/or corona-treated;    -   optionally, at least one, preferably plasma and/or        corona-treated, conversion layer;    -   optionally, a polysiloxane layer, in particular obtained by use        of plasma polymerisation of at least one organosilicon compound,        which is preferably plasma and/or corona-treated,    -   optionally, at least one, preferably plasma and/or        corona-treated and/or coloured primer layer;    -   optionally, a polysiloxane layer, in particular obtained by use        of plasma polymerisation of at least one organosilicon compound,        which is preferably plasma and/or corona-treated,    -   at least one matt, in particular colour, coating, such as a matt        paint, in particular with gloss grade “medium gloss” (G2),        preferably with gloss grade “matt” (G3), respectively determined        according to DIN EN ISO 2813:2014 (issue date: 2015-02) or at        least one gloss, in particular colour, coating, such as a gloss        paint, in particular with gloss grade “glossy” (G1), determined        according to DIN EN ISO 2813:2014 (issue date: 2015-02),        preferably the matt coating;    -   a metallic layer obtained using vapour deposition and/or        sputtering technology, preferably plasma and/or corona-treated,        containing or consisting of a first metal, selected from the        group consisting of aluminium, silver, gold, lead, vanadium,        manganese, magnesium, iron, cobalt, molybdenum, tungsten,        nickel, copper, chromium, palladium, platinum, titanium,        zirconium and zinc, in particular aluminium, or containing or        consisting of a first metal alloy, selected from the group        consisting of brass, bronze, steel, in particular special steel        or stainless steel, alloys of aluminium, magnesium and titanium,        in particular an aluminium layer;    -   preferably a polysiloxane layer, in particular obtained by use        of plasma polymerisation of at least one organosilicon compound,        which is preferably plasma and/or corona-treated,    -   at least one, in particular transparent and/or coloured,        overcoat, preferably on the treated polysiloxane layer.

The metallic layer adjacent to the cover layer, in particular thealuminium layer, is advantageously not transparent and not translucentfor visible light.

With the coated metallic substrate described above, such an embodimentis preferred in which a polysiloxane layer is present between themetallic layer and the coating layer which is obtained by use of plasmapolymerisation of at least one organosilicon compound, which has alsobeen plasma and/or corona-treated.

The object that forms the basis of the invention is finally alsoattained by a coated metallic substrate, in particular obtained orobtainable according to a method according to the invention, comprising,in this order,

-   -   a, in particular plasma and/or corona-treated and/or purified,        metallic substrate;    -   optionally, a metallic layer obtained by use of vapour        deposition and/or sputtering technology, which is preferably        plasma and/or corona-treated, containing or consisting of a        second metal selected from the group consisting of titanium,        hafnium and zirconium, in particular zirconium, or selected from        a second metal alloy from the group consisting of titanium,        hafnium and zirconium alloys;    -   optionally, a polysiloxane layer, in particular obtained by use        of plasma polymerisation of at least one organosilicon compound,        which is preferably plasma and/or corona-treated;    -   optionally, at least one, preferably plasma and/or        corona-treated, conversion layer;    -   optionally, a polysiloxane layer, in particular obtained by use        of plasma polymerisation of at least one organosilicon compound,        which is preferably plasma and/or corona-treated;    -   optionally, at least one, preferably plasma and/or        corona-treated and/or coloured primer layer;    -   optionally, a polysiloxane layer, in particular obtained by use        of plasma polymerisation of at least one organosilicon compound,        which is preferably plasma and/or corona-treated;    -   preferably, at least one, preferably plasma and/or        corona-treated, colour layer;    -   a metallic layer obtained by use of vapour deposition and/or        sputtering technology, preferably plasma and/or corona-treated,        containing or consisting of a first metal, selected from the        group consisting of aluminium, silver, gold, lead, vanadium,        manganese, magnesium, iron, cobalt, molybdenum, tungsten,        nickel, copper, chromium, palladium, platinum, titanium,        zirconium and zinc, in particular aluminium, or containing or        consisting of a first metal alloy, selected from the group        consisting of brass, bronze, steel, in particular special steel        or stainless steel, alloys of aluminium, magnesium and titanium,        with the application system, in particular an aluminium layer,        which is transparent or translucent for visible light;    -   preferably a polysiloxane layer, in particular obtained by use        of plasma polymerisation of at least one organosilicon compound,        which is preferably plasma and/or corona-treated,    -   at least one, in particular transparent and/or coloured,        overcoat, preferably on the treated polysiloxane layer.

The metallic layer adjacent to the cover layer here, in particular thealuminium layer, is here preferably present in an average, in particularabsolute, thickness in the range of 1 nm to 50 nm, preferably in therange of 10 nm to 40 nm, and particularly preferred in the range of 15nm to 30 nm.

With the coated metallic substrate described above, such an embodimentis preferred in which a polysiloxane layer is present between themetallic layer and the coating layer which is obtained by use of plasmapolymerisation of at least one organosilicon compound, which has alsobeen plasma and/or corona-treated.

Additionally, such an embodiment variant is preferred in which adjacentto the metallic layer obtained by use of the vapour deposition and/orsputtering technology, the colour layer, the colour or colouredpolysiloxane layer, the colour or coloured primer layer of the colour orcoloured conversion layer is present.

Here, in an advantageous design, the metallic substrate, the at leastone metallic layer, the at least one polysiloxane layer, the conversionlayer, the primer layer, the matt or glossy coating, the colour layerand/or the overcoat, in particular the matt or glossy layering or thecolour layer, has a structured surface.

For the colour layer, such as the one that could be used in method stepsjj-kk and PP-QQ and as can be found in the coated substrates obtainablein accordance with the method according to the invention, recourse canbe made to 2K lacquer systems, 1K lacquer systems and UV lacquersystems.

An application system for the application of a metallic layer iscomprised or represented by a vacuum vapour deposition system with avacuum chamber, and at least one, in particular a plurality of, firstheatable reception units, in particular trays, boat elements or helicalshafts, in each case operatively coupled with a first heating device orcomprising or representing a first heating device, in each caseconfigured and suitable for the reception of a first metal or a firstmetal alloy with a first melting point or melting range, and at leastone, in particular a plurality of, second heatable reception units, inparticular trays, boat elements, or helical shafts, in each caseoperatively coupled with a second heating device or comprising orrepresenting a second heating device, in each case configured andsuitable for the reception of a second metal or a second metal alloywith a second melting point or melting range, wherein the first meltingpoint or the first melting range are different from the second meltingpoint or second melting range, and, in addition, a control device forthe adjustment of first and second temperatures in such a way that thefirst and the second metal or the first and second metal alloy evaporateessentially simultaneously or overlapping in time (co-evaporation).

Here, provision can be made in one embodiment variant that theapplication system for the application of a metallic layer comprises atleast one first container, located in particular outside the vacuumchamber of the vacuum vapour deposition system, for receiving a firstorganosilicon compound, with a feed line to the vacuum chamber, and atleast one second container, located in particular outside the vacuumchamber of the vacuum vapour deposition system for receiving a secondorganosilicon compound, with a feed line to the vacuum chamber.

It has proved particularly purposeful for the application system for theapplication of a metallic layer to be also equipped with at least oneframe, in particular arranged within the vacuum chamber, with alongitudinal orientation and with at least one support, in particular inthe form of a shaft, which is aligned essentially along the longitudinalorientation of the frame, designed and configured to receive at leastone, in particular a plurality of, non-metallic and/or metallicsubstrates, wherein the frame and/or the at least one support is/arecapable of being rotated about an axis. Suitable frames which can beused with the application system can be found, for example, in EP 2 412445 and DE 20 2007 016 072.

The non-metallic and metallic substrates which are obtainable with themethod according to the invention can be used, for example, asaccessories for automobile manufacture, motorcycle manufacture, bicyclemanufacture or shipbuilding, for rims, in particular light metal alloyrims, wheels, in particular light metal alloy wheels, or as aconstituent part thereof, for sanitary installation objects, inparticular as a tap or mixer, or as a constituent part thereof, forautomobile body internal or external components or as a constituent partthereof, for handles or handle components, in particular door handles,or as a constituent part thereof, for profiles or frames, in particularwindow frames, or as a constituent part thereof, for fittings systems oras a constituent part thereof, in particular signs and door signs, forhousings or as packing or as a constituent part thereof, for internal orexternal components of ships or as a constituent part thereof, forjewellery items or as a constituent part thereof, for high-qualitystructural components or as a constituent part thereof, for indoor oroutdoor furniture items, such as kitchen, office or home furniture, fordomestic appliances, in particular coffee-making machines, or as aconstituent part thereof, for internal or external components ofaircraft or as a constituent part thereof, for internal or externalcomponents of buildings or as a constituent part thereof, for heatingelements or pipes or as a constituent part thereof, for elevatorcomponents or as a constituent part thereof, for parts of electroniccomponents or devices or as a constituent part thereof, for componentsof kitchen appliances, for example coffee-making machines, or as a partof communications components or devices, in particular mobiletelephones, or as a constituent part thereof.

Additionally, the object that forms the basis of the invention isattained by a method for producing a coated non-metallic substrate, inparticular a plastic substrate, comprising

-   -   a) provision of a non-metallic substrate, in particular a        plastic substrate, with at least one surface which is capable of        being coated at least in part areas,    -   c) provision of at least one plasma generator and/or at least        one corona system,    -   d) optionally, plasma treatment with the plasma generator and/or        corona treatment of the non-metallic substrate, in particular        plastic substrate, or of the coatable surface of the        non-metallic substrate, in particular plastic substrate,    -   e) optionally, treating of the non-metallic substrate, in        particular plastic substrate, obtained according to step a) or        d), or of the coatable surface of the non-metallic substrate, in        particular plastic substrate, with at least one organosilicon        compound, in particular by use of plasma polymerization, thus        forming a polysiloxane layer,    -   f) optionally, plasma treatment with the plasma generator and/or        corona treatment of the polysiloxane layer in accordance with        step e),    -   g) optionally, applying at least one, optionally coloured,        primer layer onto the non-metallic substrate, in particular        plastic substrate, or onto the coatable surface of the        non-metallic substrate, in particular plastic substrate, in        accordance with step a) or d), or onto the polysiloxane layer in        accordance with step e) or f),    -   h) optionally, plasma treatment with the plasma generator and/or        corona treatment of the primer layer in accordance with step g),    -   i) optionally, treating the primer layer obtained according to        step g) or h) with at least one organosilicon compound, in        particular by use of plasma polymerization, thus forming a        polysiloxane layer,    -   j) optionally, plasma treatment with the plasma generator and/or        corona treatment of the polysiloxane layer in accordance with        step i),    -   j-k) applying at least one matt, in particular colour, coating,        such as a matt lacquer, in particular with gloss grade “medium        gloss” (G2) or preferably with gloss grade “matt” (G3),        respectively determined according to DIN EN ISO 2813:2014 (issue        date: 2015-02) or applying at least one gloss, in particular        colour, coating, such as a gloss lacquer, in particular with        gloss grade “glossy” (G1), determined according to DIN EN ISO        2813:2014 (issue date: 201502), preferably applying the matt        coating,    -   k″) opaque application of at least one effect lacquer with a        metallic colour impression,    -   l) optionally, plasma treatment with the plasma generator and/or        corona treatment of the effect layer in accordance with step        k″),    -   m) preferably treating the effect layer obtained according to        step k″) or l) with at least one organosilicon compound, in        particular by use of plasma polymerization, thus forming a        polysiloxane layer,    -   n) preferably plasma treatment with the plasma generator and/or        corona treatment of the polysiloxane layer in accordance with        step m), and    -   o) applying at least one, in particular transparent and/or        coloured, overcoat onto the layer in accordance with steps k″),        l), m) or n), in particular onto the treated polysiloxane layer        in accordance with step n).

The method described above differs from the corresponding methodaccording to the invention in that step k) has been replaced by step k″)(opaque application of at least one effect lacquer with a metalliccolour impression). In the same manner, the coated non-metallicsubstrates obtainable according to the method described above differfrom those coated non-metallic substrates obtainable according to thecorresponding method, containing step k), by the replacement of themetallic layer by the effect lacquer which is opaquely applied, with ametallic colour impression. The general and preferred specific featuresand embodiment variants, which have been described above for the methodcontaining step k) and the coated products obtainable according to thismethod, apply in the same manner to the method containing step k″) orthe coated products obtainable according to this method.

Additionally, the object that forms the basis of the invention isattained by a method for producing a coated non-metallic substrate, inparticular a plastic substrate, comprising

-   -   a) provision of a non-metallic substrate, in particular a        plastic substrate, with at least one surface which is capable of        being coated at least in part areas,    -   c) provision of at least one plasma generator and/or at least        one corona system,    -   d) optionally, plasma treatment with the plasma generator and/or        corona treatment of the non-metallic substrate, in particular        plastic substrate, or of the coatable surface of the        non-metallic substrate, in particular plastic substrate,    -   e) optionally, treating of the non-metallic substrate, in        particular plastic substrate, obtained according to step a) or        d), or of the coatable surface of the non-metallic substrate, in        particular plastic substrate, with at least one organosilicon        compound, in particular by use of plasma polymerization, thus        forming a polysiloxane layer,    -   f) optionally, plasma treatment with the plasma generator and/or        corona treatment of the polysiloxane layer in accordance with        step e),    -   g) optionally, applying at least one, in particular coloured,        primer layer onto the non-metallic substrate, in particular        plastic substrate, or onto the coatable surface of the        non-metallic substrate, in particular plastic substrate, in        accordance with step a) or d), or onto the polysiloxane layer in        accordance with step e) or f),    -   h) optionally, plasma treatment with the plasma generator and/or        corona treatment of the primer layer in accordance with step g),    -   i) optionally, treating the primer layer obtained according to        step g) or h) with at least one organosilicon compound, in        particular by use of plasma polymerization, thus forming a        polysiloxane layer,    -   j) optionally, plasma treatment with the plasma generator and/or        corona treatment of the polysiloxane layer in accordance with        step i),    -   jj-kk) preferably applying at least one colour layer onto the        non-metallic substrate or the coatable surface of the        non-metallic substrate according to step a) or d) or onto the        polysiloxane layer according to step e) or f), or onto the        primer layer according to step g) or h), or onto the        polysiloxane layer according to step i) or j),    -   k′″) applying at least one effect lacquer with metallic colour        impression such that the obtained coating is transparent or        translucent for visible light,    -   l) optionally, plasma treatment with the plasma generator and/or        corona treatment of the effect layer in accordance with step        k′″),    -   m) preferably treating the effect layer obtained according to        step k′″) or l) with at least one organosilicon compound, in        particular by use of plasma polymerization, thus forming a        polysiloxane layer,    -   n) preferably plasma treatment with the plasma generator and/or        corona treatment of the polysiloxane layer in accordance with        step m), and    -   o) o) applying at least one, in particular transparent and/or        coloured, overcoat onto the layer in accordance with steps k′″),        l), m) or n), in particular onto the treated polysiloxane layer        in accordance with step n).

The method described above differs from the corresponding methodaccording to the invention in that step k′) has been replaced by stepk′″) (application of at least one effect lacquer such that the obtainedcoating is transparent or translucent for visible light). In the samemanner, the coated non-metallic substrates obtainable according to themethod described above differ from those coated non-metallic substratesobtainable according to the corresponding method, containing step k′),by the replacement of the metallic layer by the effect lacquer which isapplied with a metallic colour impression such that it is transparent ortranslucent for visible light. The general and preferred specificfeatures and embodiment variants, which have been described above forthe method containing step k′) and the coated products obtainableaccording to this method, apply in the same manner to the methodcontaining step k′″) or the coated products obtainable according to thismethod.

Additionally, the object that forms the basis of the invention isattained by a method for producing a coated metallic substrate,comprising

-   -   A) provision of a metallic substrate with at least one surface        which is capable of being coated at least in part areas,    -   C) provision of at least one plasma generator and/or at least        one corona system,    -   D) optionally, cleaning of the metallic substrate or of the        coatable surface of the metallic substrate,    -   E) optionally, applying at least one metallic layer, containing        or consisting of a second metal, selected from the group        consisting of titanium, hafnium and zirconium, in particular        zirconium, or of a second metal alloy, selected from the group        consisting of alloys of titanium, hafnium and zirconium, with        the application system, in particular by use of vapour        deposition and/or sputtering technology, onto the metallic        substrate or the coatable surface of the metallic substrate in        accordance with step A) or D),    -   F) optionally, plasma treatment with the plasma generator and/or        corona treatment of the metallic substrate or of the coatable        surface of the metallic substrate in accordance with step A) or        D), or of the metallic layer in accordance with step E),    -   G) optionally, treating the metallic substrate obtained        according to step A) or D), or treating the coatable surface of        the metallic substrate obtained according to step A) or D) or of        the metallic layer obtained according to step E) or F) with at        least one organosilicon compound, in particular by use of plasma        polymerization, thus forming a polysiloxane layer,    -   H) optionally, plasma treatment with the plasma generator and/or        corona treatment of the polysiloxane layer in accordance with        step G),    -   I) optionally, applying a conversion layer onto the metallic        substrate or the coatable surface of the metallic substrate in        accordance with step A) or D), or onto the metallic layer in        accordance with step E) or F), or onto the polysiloxane layer in        accordance with step G) or H),    -   J) optionally, plasma treatment with the plasma generator and/or        corona treatment of the conversion layer in accordance with step        I),    -   K) optionally, treating the conversion layer obtained according        to step I) or J) with at least one organosilicon compound, in        particular by use of plasma polymerization, thus forming a        polysiloxane layer,    -   L) optionally, plasma treatment with the plasma generator and/or        corona treatment of the treated polysiloxane layer obtained        according to step K),    -   M) optionally, applying at least one, optionally coloured,        primer layer onto the metallic substrate or the coatable surface        of the metallic substrate in accordance with step A) or D), or        onto the metallic layer in accordance with step E) or F), or        onto the polysiloxane layer in accordance with step G) or H), or        onto the conversion layer in accordance with step I) or J), or        onto the polysiloxane layer in accordance with step K) or L),    -   N) optionally, plasma treatment with the plasma generator and/or        corona treatment of the primer layer in accordance with step M),    -   O) optionally, treating the primer layer obtained according to        step M) or N) with at least one organosilicon compound, in        particular by use of plasma polymerization, thus forming a        polysiloxane layer,    -   P) optionally, plasma treatment with the plasma generator and/or        corona treatment of the treated polysiloxane layer obtained        according to step O),    -   P-Q) applying at least one matt, in particular colour, coating,        such as a matt lacquer, in particular with gloss grade “medium        gloss” (G2) or preferably with gloss grade “matt” (G3),        respectively determined according to DIN EN ISO 2813:2014 (issue        date: 2015-02) or applying at least one gloss, in particular        colour, coating, such as a gloss lacquer, in particular with        gloss grade “glossy” (G1), determined according to DIN EN ISO        2813:2014 (issue date: 201502), preferably applying the matt        coating,    -   Q″) opaque application of at least one effect lacquer with a        metallic colour impression,    -   R) optionally, plasma treatment with the plasma generator and/or        corona treatment of the effect layer in accordance with step        Q″),    -   S) preferably treating the effect layer obtained according to        step Q″) or R) with at least one organosilicon compound, in        particular by use of plasma polymerization, thus forming a        polysiloxane layer,    -   T) preferably plasma treatment with the plasma generator and/or        corona treatment of the polysiloxane layer in accordance with        step S), and    -   U) applying at least one, in particular transparent and/or        coloured overcoat onto the layer in accordance with step Q″),        R), S) or T), in particular onto the treated polysiloxane layer        according to step T).

The method described above differs from the corresponding methodaccording to the invention in that step Q) has been replaced by step Q″)(opaque application of at least one effect lacquer with a metalliccolour impression). In the same manner, the coated non-metallicsubstrates obtainable according to the method described above differfrom those coated metallic substrates obtainable according to thecorresponding method, containing step Q), by the replacement of themetallic layer by the effect lacquer which is opaquely applied, with ametallic colour impression. The general and preferred specific featuresand embodiment variants, which have been described above for the methodcontaining step Q) and the coated products obtainable according to thismethod, apply in the same manner to the method containing step Q″) orthe coated products obtainable according to this method.

Finally, the object that forms the basis of the invention is attained bya method for producing a coated metallic substrate, comprising

-   -   A) provision of a metallic substrate with at least one surface        which is capable of being coated at least in part areas,    -   C) provision of at least one plasma generator and/or at least        one corona system,    -   D) optionally, cleaning of the metallic substrate or of the        coatable surface of the metallic substrate,    -   E) optionally, applying at least one metallic layer, containing        or consisting of a second metal, selected from the group        consisting of titanium, hafnium and zirconium, in particular        zirconium, or of a second metal alloy, selected from the group        consisting of alloys of titanium, hafnium and zirconium, with        the application system, in particular by use of vapour        deposition and/or sputtering technology, onto the metallic        substrate or the coatable surface of the metallic substrate in        accordance with step A) or D),    -   F) optionally, plasma treatment with the plasma generator and/or        corona treatment of the metallic substrate or of the coatable        surface of the metallic substrate in accordance with step A) or        D), or of the metallic layer in accordance with step E),    -   G) optionally, treating the metallic substrate obtained        according to step A) or D), or treating the coatable surface of        the metallic substrate obtained according to step A) or D) or of        the metallic layer obtained according to step E) or F) with at        least one organosilicon compound, in particular by use of plasma        polymerization, thus forming a polysiloxane layer,    -   H) optionally, plasma treatment with the plasma generator and/or        corona treatment of the polysiloxane layer in accordance with        step G),    -   I) optionally, applying a conversion layer onto the metallic        substrate or the coatable surface of the metallic substrate in        accordance with step A) or D), or onto the metallic layer in        accordance with step E) or F), or onto the polysiloxane layer in        accordance with step G) or H),    -   J) optionally, plasma treatment with the plasma generator and/or        corona treatment of the conversion layer in accordance with step        I),    -   K) optionally, treating the conversion layer obtained according        to step I) or J) with at least one organosilicon compound, in        particular by use of plasma polymerization, thus forming a        polysiloxane layer,    -   L) optionally, plasma treatment with the plasma generator and/or        corona treatment of the treated polysiloxane layer obtained        according to step K),    -   M) optionally, applying at least one, preferably coloured,        primer layer onto the metallic substrate or the coatable surface        of the metallic substrate in accordance with step A) or D), or        onto the metallic layer in accordance with step E) or F), or        onto the polysiloxane layer in accordance with step G) or H), or        onto the conversion layer in accordance with step I) or J), or        onto the polysiloxane layer in accordance with step K) or L),    -   N) optionally, plasma treatment with the plasma generator and/or        corona treatment of the primer layer in accordance with step M),    -   O) optionally, treating the primer layer obtained according to        step M) or N) with at least one organosilicon compound, in        particular by use of plasma polymerization, thus forming a        polysiloxane layer,    -   P) optionally, plasma treatment with the plasma generator and/or        corona treatment of the treated polysiloxane layer obtained        according to step O),

-   PP-QQ) preferably, applying at least one colour layer onto the    metallic substrate or the coatable surface of the metallic substrate    in accordance with step A) or D), or onto the metallic layer in    accordance with step E) or F), or onto the polysiloxane layer in    accordance with step G) or H), or onto the conversion layer in    accordance with step I) or J), or onto the polysiloxane layer in    accordance with step K) or L), or onto the primer layer according to    step M) or N), or onto the polysiloxane layer according to step O)    or P),

-   Q′″) applying at least one effect lacquer with metallic colour    impression such that the obtained coating is transparent or    translucent for visible light,    -   R) R) optionally, plasma treatment with the plasma generator        and/or corona treatment of the effect layer in accordance with        step Q′″),    -   S) S) treating the effect layer obtained according to step Q′″)        or R) with at least one organosilicon compound, in particular by        use of plasma polymerization, thus forming a polysiloxane layer,    -   T) T) plasma treatment with the plasma generator and/or corona        treatment of the polysiloxane layer in accordance with step S),        and    -   U) U) applying at least one, in particular transparent and/or        coloured, overcoat onto the layer in accordance with steps Q′″),        R), S) or T), in particular onto the treated polysiloxane layer        in accordance with step T).

The method described above differs from the corresponding methodaccording to the invention in that step Q′) has been replaced by stepQ′″) (application of at least one effect lacquer such that the obtainedcoating is transparent or translucent for visible light). In the samemanner, the coated metallic substrates obtainable according to themethod described above differ from those coated metallic substratesobtainable according to the corresponding method, containing step Q′),by the replacement of the metallic layer by the effect lacquer which isapplied with a metallic colour impression such that it is transparent ortranslucent for visible light. The general and preferred specificfeatures and embodiment variants, which have been described above forthe method containing step Q′) and the coated products obtainableaccording to this method, apply in the same manner to the methodcontaining step Q′″) or the coated products obtainable according to thismethod.

Effect lacquers that provide a metallic appearance are known to a personskilled in the art. Such effect lacquers regularly use so-calledmetallic effect pigments or metal pigments, e.g. based on aluminium.Suitable effect lacquers or effect pigments are described e.g. in DE 102007 007908, WO 2004/026971, WO 2004/026972, DE 4422287 and DE 19505161.A further example of effect and chromium lacquers by Endlendt Color,D-16775 Sonnenberg, is e.g. disclosed in WO 2008/046567 A 1, andreference is made to HS effect lacquers by Holtmann & Stierle ChemieGmbH, D-32130 Enger.

The invention is based on the surprising finding that with thesubstrates obtainable in accordance with the method according to theinvention, surfaces with a matt metallic appearance can equally beobtained as colourful metallic surfaces, and in a simple and reliable,i.e. low-cost, manner. The methods according to the invention are easilysuitable for mass production. They make it possible to develop entirelynew fields of application for plastic and metallic substrates.Furthermore, with the method according to the invention or with theproducts according to the invention, a high-quality coloured glossycoating can be provided that permanently retains its gloss. In addition,the coated non-metallic and metallic substrates obtainable with themethod according to the invention are provided with excellent corrosionresistance. The coated substrates obtainable with the methods accordingto the invention are further characterized by very good adherence.Accordingly, these coated substrates exhibit outstanding resistance tocorrosion even when the surfaces have suffered mechanical damage, forexample by stone impact or scratching. It is also advantageous that withthe substrates according to the invention with a matt appearance, noimpairment to the surface can be detected with mechanical stress. Afurther advantage which is inherent with the method according to theinvention is that only very short changeover times are required in orderto coat new substrate batches. Furthermore, the method according to theinvention allows the scope of the entire system for manufacturing coatedsubstrates with a colourful or matt appearance, starting from thesubstrate which has not yet been cleaned and is to be coated, to besubstantially reduced, such that a significantly reduced space isrequired in relation to conventional systems. In addition, it ispossible with the methods according to the invention to substantiallyreduce the processing time up to completion of the coated substrateready for sale. Reduced cycle times are necessarily inherent with this.

The features of the invention disclosed in the foregoing description andin the claims can be essential for the implementation of the inventionin its different embodiments, both individually as well as in anycombination.

1-25. (canceled)
 26. A method for manufacturing a coated metallicsubstrate, comprising: A) providing a metallic substrate with at leastone surface that is capable of being coated at least in part areas; B)providing an application system for applying a metallic layer to the atleast one surface of the metallic substrate; C) providing at least oneplasma generator and/or at least one corona system within theapplication system; D) cleaning the coatable surface of the metallicsubstrate; E) applying, with the application system, at least onemetallic layer containing a second metal selected from the groupconsisting of titanium, hafnium and zirconium, or a second metal alloyselected from the group consisting of alloys of titanium, hafnium andzirconium, onto the coatable surface of the metallic substrate; F)treating, by plasma treatment and/or corona treatment, the coatablesurface of the metallic substrate or the metallic layer applied to thecoatable surface of the metallic substrate according to step E); G)treating the coatable surface of the metallic substrate or the metalliclayer applied to the coatable surface of the metallic substrate with atleast one organosilicon compound by way of plasma polymerization to forma polysiloxane layer; H) treating, by plasma treatment and/or coronatreatment, the polysiloxane layer formed according to step G); I)applying a conversion layer onto at least one of the coatable surface ofthe metallic substrate, the metallic layer applied according to step E),or the polysiloxane layer formed according to step G); J) treating, byplasma treatment and/or corona treatment, the conversion layer; K)treating the conversion layer with at least one organosilicon compoundby way of plasma polymerization to form a treated polysiloxane layer; L)treating, by plasma treatment and/or corona treatment, the treatedpolysiloxane layer formed according to step K); M) applying at least oneprimer layer onto at least one of the coatable surface of the metallicsubstrate, the metallic layer applied according to step E), thepolysiloxane layer formed according to step G), the conversion layer, orthe treated polysiloxane layer formed according to step K); N) treating,by plasma treatment and/or corona treatment, the primer layer; O)treating the primer layer with at least one organosilicon compound byway of plasma polymerization to form a polysiloxane layer; P) treating,by plasma treatment and/or corona treatment, the polysiloxane layerformed according to step 0); P-Q) applying at least one matt coating orapplying at least one gloss coating; Q) applying, with the applicationsystem, at least one metallic layer containing a first metal selectedfrom the group consisting of aluminum, silver, gold, lead, vanadium,manganese, magnesium, iron, cobalt, molybdenum, tungsten, nickel,copper, chromium, palladium, platinum, titanium, zirconium and zinc, orcontaining a first metal alloy selected from the group consisting ofbrass, bronze, steel, alloys of aluminum, magnesium and titanium, ontothe primer layer; R) treating, by plasma treatment and/or coronatreatment, the metallic layer applied according to step Q); S) treatingthe metallic layer applied according to step Q) with at least oneorganosilicon compound by way of plasma polymerization to form apolysiloxane layer; T) treating, by plasma treatment and/or coronatreatment, the polysiloxane layer formed according to step S); and U)applying at least one transparent and/or colored overcoat onto themetallic layer applied according to step Q) or onto the polysiloxanelayer treated according to step T).
 27. The method according to claim26, wherein in step Q) the metallic layer is applied with a thicknesssuch that the metallic layer is not transparent and is not translucentfor visible light.
 28. The method according to claim 26, wherein stepsS) and T) are conducted prior to step U).
 29. A method for manufacturinga coated metallic substrate, comprising: A) providing a metallicsubstrate with at least one surface that is capable of being coated atleast in part areas; B) providing an application system for applying ametallic layer to the at least one surface of the metallic substrate; C)providing at least one plasma generator and/or at least one coronasystem within the application system; D) cleaning the coatable surfaceof the metallic substrate; E) applying, with the application system, atleast one metallic layer containing a second metal selected from thegroup consisting of titanium, hafnium and zirconium, or a second metalalloy selected from the group consisting of alloys of titanium, hafniumand zirconium, onto the coatable surface of the metallic substrate; F)treating, by plasma treatment or corona treatment, the coatable surfaceof the metallic substrate or the metallic layer applied to the coatablesurface of the metallic substrate according to step E); G) treating thecoatable surface of the metallic substrate or the metallic layer appliedto the coatable surface of the metallic substrate with at least oneorganosilicon compound by way of plasma polymerization to form apolysiloxane layer; H) treating, by plasma treatment and/or coronatreatment, the polysiloxane layer formed according to step G); I)applying a conversion layer onto at least one of the coatable surface ofthe metallic substrate, the metallic layer applied according to step E),or the polysiloxane layer formed according to step G); J) treating, byplasma treatment and/or corona treatment, the conversion layer; K)treating the conversion layer with at least one organosilicon compound,by way of plasma polymerization, to form a treated polysiloxane layer;L) treating, by plasma treatment and/or corona treatment, the treatedpolysiloxane layer formed according to step K); M) applying at least oneprimer layer onto at least one of the coatable surface of the metallicsubstrate, the metallic layer applied according to step E), thepolysiloxane layer formed according to step G), the conversion layer, orthe treated polysiloxane layer formed according to step K); N) treating,by plasma treatment and/or corona treatment, the primer layer; O)treating the primer layer with at least one organosilicon compound, byway of plasma polymerization, to form a polysiloxane layer; P) treating,by plasma treatment and/or corona treatment, the polysiloxane layerformed according to step 0); Q′) applying, with the application system,at least one metallic layer containing a first metal selected from thegroup consisting of aluminum, silver, gold, lead, vanadium, manganese,magnesium, iron, cobalt, molybdenum, tungsten, nickel, copper, chromium,palladium, platinum, titanium, zirconium and zinc, or containing a firstmetal alloy selected from the group consisting of brass, bronze, steel,alloys of aluminum, magnesium and titanium, onto at least one of thecoatable surface of the metallic substrate, the metallic layer appliedaccording to step E), the polysiloxane layer formed according to stepG), the conversion layer, the polysiloxane layer, the primer layer, orthe treated polysiloxane layer formed according to step K), whereby themetallic layer is applied in a thickness such that the metallic layer istransparent or translucent for visible light; R) treating, by plasmatreatment and/or corona treatment, the metallic layer applied accordingto step Q′); S) treating the metallic layer obtained according to stepQ) with at least one organosilicon compound by way of plasmapolymerization to form a polysiloxane layer; T) treating, by plasmatreatment and/or corona treatment, the polysiloxane layer formedaccording to step S); and U) applying at least one transparent and/orcolored overcoat onto the layer applied according to step Q′) or ontothe polysiloxane layer treated according to step T).
 30. The methodaccording to claim 29, further comprising: PP-QQ) applying at least onecolor layer onto at least one of the coatable surface of the metallicsubstrate, the metallic layer, the polysiloxane layer, the conversionlayer, the treated polysiloxane layer according to step K) or L), theprimer layer, or the treated polysiloxane layer according to step O) orP).
 31. The method according to claim 29, wherein the metallic layer isapplied in an average thickness in a range of 1 nm to 50 nm.
 32. Themethod according to claim 31, wherein the metallic layer is applied inan average thickness in a range of 10 nm to 40 nm.
 33. The methodaccording to claim 32, wherein the metallic layer is applied in anaverage thickness in a range of 15 nm to 30 nm.
 34. The method accordingto claim 29, wherein steps S) and T) are conducted prior to step U). 35.The method according to claim 30, wherein a layer according to stepPP-QQ), a color polysiloxane layer, a color primer layer, or a colorconversion layer is adjacent to and in contact with the layer appliedaccording to step Q′).
 36. The method according to claim 26, wherein thesteps D), M), N), P-Q), Q), S), T) and U) respectively follow eachother.
 37. The method according to claim 29, wherein the steps D), M),N), Q′), S), T) and U) respectively follow each other.
 38. The methodaccording to claim 30, wherein the steps D), M), N), PP-QQ), Q′), S), T)and U) respectively follow each other.
 39. The method according to claim26, wherein the steps D), M), N), O), P-Q), Q), S), T) and U)respectively follow each other.
 40. The method according to claim 29,wherein the steps D), M), N), O), Q′), S), T) and U) respectively followeach other.
 41. The method according to claim 30, wherein the steps D),M), N), O), PP-QQ), Q′), S), T) and U) respectively follow each other.42. The method according to claim 26, wherein the steps D), E), F,), M),P-Q), Q), S), T) and U) respectively follow each other.
 43. The methodaccording to claim 29, wherein the steps D), E), F,), M), Q′), S), T)and U) respectively follow each other.
 44. The method according to claim30, wherein the steps D), E), F,), M), PP-QQ), Q′), S), T) and U)respectively follow each other.
 45. The method according to claim 26,wherein the steps D), E), F,), M), O), P-Q), Q), S), T) and U)respectively follow each other.
 46. The method according to claim 29,wherein the steps D), E), F,), M), O), Q′), S), T) and U) respectivelyfollow each other.
 47. The method according to claim 30, wherein thesteps D), E), F,), M), O), PP-QQ), Q′), S), T) and U) respectivelyfollow each other.
 48. The method according to claim 26, wherein thesteps D), G), H), M), P-Q), Q), S), T) and U) respectively follow eachother.
 49. The method according to claim 29, wherein the steps D), G),H), M), Q′), S), T) and U) respectively follow each other.
 50. Themethod according to claim 30, wherein the steps D), G), H), M), PP-QQ),Q′), S), T) and U) respectively follow each other.
 51. The methodaccording to claim 26, wherein the step D), G), H), M), O), P-Q), Q),S), T) and U) respectively follow each other.
 52. The method accordingto claim 29, wherein the steps D), G), H), M), O), Q′), S), T) and U)respectively follow each other.
 53. The method according to claim 30,wherein the steps D), G), H), M), O), PP-QQ), Q′), S), T) and U)respectively follow each other.
 54. The method according to claim 26,wherein the steps D), E), G), H), M), P-Q), Q), S), T) and U)respectively follow each other.
 55. The method according to claim 29,wherein the steps D), E), G), H), M), Q′), S), T) and U) respectivelyfollow each other.
 56. The method according to claim 30, wherein thesteps D), E), G), H), M), PP-QQ), Q′), S), T) and U) respectively followeach other.
 57. The method according to claim 26, wherein the steps D),E), G), H), M), O), P-Q), Q), S), T) and U) respectively follow eachother.
 58. The method according to claim 29, wherein the steps D), E),G), H), M), O), Q′), S), T) and U) respectively follow each other. 59.The method according to claim 30, wherein the steps D), E), G), H), M),O), PP-QQ), Q′), S), T) and U) respectively follow each other.
 60. Themethod according to claim 26, wherein the steps D), M), O), P-Q), Q),S), T) and U) respectively follow each other.
 61. The method accordingto claim 29, wherein the steps D), M), O), Q′), S), T) and U)respectively follow each other.
 62. The method according to claim 30,wherein the steps D), M), PP-QQ), Q′), S), T) and U) respectively followeach other.
 63. The method according to claim 26, wherein the steps D),M), O), P-Q), Q), S), T) and U) respectively follow each other.
 64. Themethod according to claim 29, wherein the steps D), M), O), Q′), S), T)and U) respectively follow each other.
 65. The method according to claim30, wherein the steps D), M), O), PP-QQ), Q′), S), T) and U)respectively follow each other.
 66. The method according to claim 26,wherein the steps D), G), H), P-Q), Q), S), T) and U) respectivelyfollow each other.
 67. The method according to claim 29, wherein thesteps D), G), H), Q′), S), T) and U) respectively follow each other. 68.The method according to claim 30, wherein the steps D), G), H), PP-QQ),Q′), S), T) and U) respectively follow each other.
 69. The methodaccording to claim 26, wherein the steps D), G), H), O), P-Q), Q), S),T) and U) respectively follow each other.
 70. The method according toclaim 29, wherein the steps D), G), H), O), Q′), S), T) and U)respectively follow each other.
 71. The method according to claim 30,wherein the steps D), G), H), O), PP-QQ), Q′), S), T) and U)respectively follow each other.
 72. A coated metallic substrate obtainedaccording to the method of claim 26, wherein the coated metallicsubstrate comprises, in this order: a metallic substrate; a metalliclayer that contains a second metal selected from the group consisting oftitanium, hafnium and zirconium, or a second metal alloy selected fromthe group consisting of titanium, hafnium and zirconium alloys, and isplasma or corona-treated; a polysiloxane layer obtained by way of plasmapolymerization of at least one organosilicon compound that is plasma orcorona-treated; at least one conversion layer that is plasma orcorona-treated; a polysiloxane layer obtained by way of plasmapolymerization of at least one organosilicon compound that is plasma orcorona-treated; at least one primer layer that is plasma orcorona-treated; a polysiloxane layer obtained by way of plasmapolymerization of at least one organosilicon compound that is plasma orcorona-treated; at least one matt coating or at least one gloss coating;a metallic layer that contains a first metal selected from the groupconsisting of aluminum, silver, gold, lead, vanadium, manganese,magnesium, iron, cobalt, molybdenum, tungsten, nickel, copper, chromium,palladium, platinum, titanium, zirconium and zinc, or a first metalalloy selected from the group consisting of brass, bronze, steel, alloysof aluminum, magnesium and titanium, and is plasma or corona-treated; apolysiloxane layer obtained by way of plasma polymerization of at leastone organosilicon compound that is plasma or corona-treated; and atleast one transparent and/or colored overcoat that is applied onto themetallic layer that contains the first metal or first metal alloy oronto the outermost treated polysiloxane layer.
 73. The coated metallicsubstrate according to claim 72, wherein the metallic layer adjacent tothe overcoat is not transparent and not translucent for visible light.74. A coated metallic substrate obtained according to the method ofclaim 29, wherein the coated metallic substrate comprises, in thisorder: a metallic substrate; a metallic layer that contains a secondmetal selected from the group consisting of titanium, hafnium andzirconium, or a second metal alloy selected from the group consisting oftitanium, hafnium and zirconium alloys, and is plasma or corona-treated;a polysiloxane layer obtained by way of plasma polymerization of atleast one organosilicon compound that is plasma or corona-treated; atleast one conversion layer that is plasma or corona-treated; apolysiloxane layer obtained by way of plasma polymerization of at leastone organosilicon compound that is plasma or corona-treated; at leastone primer layer that is plasma or corona-treated; a polysiloxane layerobtained by way of plasma polymerization of at least one organosiliconcompound that is plasma or corona-treated; a metallic layer thatcontains a first metal selected from the group consisting of aluminum,silver, gold, lead, vanadium, manganese, magnesium, iron, cobalt,molybdenum, tungsten, nickel, copper, chromium, palladium, platinum,titanium, zirconium and zinc, or a first metal alloy selected from thegroup consisting of brass, bronze, steel, alloys of aluminum, magnesiumand titanium, which is plasma or corona-treated; a polysiloxane layerobtained by way of plasma polymerization of at least one organosiliconcompound that is plasma or corona-treated; and at least one transparentand/or colored overcoat applied onto the treated polysiloxane layer thatis adjacent to and covers the metallic layer containing the first metalor the first metal alloy.
 75. The coated metallic substrate according toclaim 74, further comprising at least one color layer that is plasma orcorona-treated, and is adjacent to and covered by the metallic layercontaining the first metal or first metal alloy.
 76. The coated metallicsubstrate according to claim 74, wherein the metallic layer thatcontains the first metal or first metal alloy is transparent or istranslucent for visible light.
 77. The coated metallic substrateaccording to claim 74, wherein the metallic layer that contains thefirst metal or first metal alloy has an average thickness in a range of1 nm to 50 nm,
 78. The coated metallic substrate according to claim 77,wherein the metallic layer that contains the first metal or first metalalloy has an average thickness in a range of 10 nm to 40 nm,
 79. Thecoated metallic substrate according to claim 78, wherein the metalliclayer that contains the first metal or first metal alloy has an averagethickness in a range of 15 nm to 30 nm.
 80. The coated metallicsubstrate according to claim 75, wherein at least one color layer, acolor polysiloxane layer, a color primer layer, or a color conversionlayer is adjacent and in contact with the metallic layer containing thefirst metal or first metal alloy.
 81. The coated metallic substrateaccording to claim 72, wherein the metallic substrate, the metalliclayer containing the second metal or second metal alloy, a polysiloxanelayer, the conversion layer, the primer layer, the matt or glossycoating, a color layer, and/or the overcoat, has a structured surface.